EP0356144A2 - Method of producing resin articles - Google Patents
Method of producing resin articles Download PDFInfo
- Publication number
- EP0356144A2 EP0356144A2 EP89308353A EP89308353A EP0356144A2 EP 0356144 A2 EP0356144 A2 EP 0356144A2 EP 89308353 A EP89308353 A EP 89308353A EP 89308353 A EP89308353 A EP 89308353A EP 0356144 A2 EP0356144 A2 EP 0356144A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- resin
- vibration
- khz
- minutes
- reaction system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 29
- 239000011347 resin Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000009745 resin transfer moulding Methods 0.000 description 2
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/22—Component parts, details or accessories; Auxiliary operations
- B29C39/42—Casting under special conditions, e.g. vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/008—Using vibrations during moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
Definitions
- the present invention relates to a method of producing resin articles, such as polyester articles, and in particular to a method of producing fibre reinforced thermosetting polymer or cast polymer articles.
- Fibre reinforced thermosetting plastics are widely used for manufacturing a large range of components.
- Various methods can be used including open moulding, resin transfer moulding, filament winding, pultrusion, casting and pre-impregnation.
- a thermosetting polyester resin When a thermosetting polyester resin is used, conventionally the resin is caused to polymerise by the inclusion of a catalyst, such as an organic peroxide. Such reactions can take place at room temperature dependent upon the catalyst used but reaction rates are frequently increased by elevating the temperature of the reaction system.
- heating the reaction system by conventional means, such as by infra red radiation, using heated moulds or using pre-heated resin, can prove to be difficult and particularly with large components, time consuming and expensive.
- the object of this invention is to provide a method of producing resin articles, wherein the resin reaction rate may be increased.
- a method of producing resin articles from a resin reaction system comprising the step of subjecting the resin reaction system to high frequency vibration during reaction.
- the invention further provides a resin article produced from a resin reaction system subjected to high frequency vibration during reaction.
- vibration frequencies in the range of 5 to 500 KHz, preferably within the range 10-100 KHz, especially within the range 30 to 50 KHz and more especially within the range 35 to 50 KHz.
- the invention has application to any fabrication technique especially in relation to resin used in fibre reinforced plastics and is particularly useful in resin transfer moulding and similar processes where resin is caused to flow into a closed mould containing fibre reinforcement.
- the invention is also particularly useful in relation to pre-impregnated glass fabrication systems.
- a polyester resin was mixed with 25% of its weight of milled glass fibre. 1% of a 1% by weight solution of cobalt naphthenate was mixed in followed by 2% by weight of methyl ethyl ketone peroxide (50% solution). The resultant mixture was immediately poured into two identical moulds. The first of these moulds was immersed in an unstirred water bath at 22 degrees C. The second mould was simultaneously immersed in a water bath at 22 degrees C in which the water was subjected to mechanical vibrations of 35 KHz. The time taken for the first unvibrated resin to solidify was 29.5 minutes. The resin in the vibrated water bath solidified in 7.6 minutes.
- Resin containing 1% of a 1% by weight solution of cobalt naphthenate and 2% by weight of methyl ethyl ketone peroxide (50% solution) was injected into a small closed mould containing continuous filament glass mat so that the final weight ratio of resin to glass was 3:2.
- the system was allowed to gel and the time for this gellation was 33 minutes.
- the same experiment was repeated but the mould was vibrated mechanically at 30 KHz. The resin gelled in 15 minutes.
- Example 2 was repeated but with jute fibre instead of glass mat. In this Example the unvibrated sample gelled in 29 minutes and the vibrated sample gelled in 14 minutes.
- Example 2 was again repeated but with a weight ratio of resin to glass of 1:1. In this Example the resin gelled in 35 minutes when not vibrated and in 16 minutes when vibrated.
- Example 1 was repeated but using finely ground calcium carbonate instead of milled glass fibre.
- the unvibrated sample solidified in 34 minutes and the vibrated sample solidified in 16 minutes.
- a piece of glass fibre mat was impregnated with polyester resin containing 0.5% of a 1% by weight solution of cobalt naphthenate and 0.75% by weight methyl ethyl ketone peroxide.
- the pre-impregnated mat was quickly sealed in a water impermeable film and forced against the inside of a clay pipe.
- the pipe was filled with water at 20 degrees C and the water was subjected to vibration of 50 KHz. The system gelled in 15 minutes. An equivalent system but without vibration gelled in 27 minutes.
- Example 6 was repeated but the catalyst was replaced with 0.75% by weight of Trigonox 42S - t-butyl perisononanoate and 0.75% by weight Perkadox 16 - bis - (4t-butylcyclohexyl) peroxy dicarbonate. In this case the water was warmed to 35 degrees C. The sample vibrated at 35 KHz gelled in 11 minutes, an unvibrated sample gelled in 21 minutes.
- Example 7 was repeated except that the system was vibrated at 50 KHz. In this case the resin gelled in 8 minutes compared with 11 minutes for a sample vibrated at 35 KHz and 21 minutes for an unvibrated sample.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Reinforced Plastic Materials (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
Abstract
Description
- The present invention relates to a method of producing resin articles, such as polyester articles, and in particular to a method of producing fibre reinforced thermosetting polymer or cast polymer articles.
- Fibre reinforced thermosetting plastics, for example, are widely used for manufacturing a large range of components. Various methods can be used including open moulding, resin transfer moulding, filament winding, pultrusion, casting and pre-impregnation. When a thermosetting polyester resin is used, conventionally the resin is caused to polymerise by the inclusion of a catalyst, such as an organic peroxide. Such reactions can take place at room temperature dependent upon the catalyst used but reaction rates are frequently increased by elevating the temperature of the reaction system. However, heating the reaction system by conventional means, such as by infra red radiation, using heated moulds or using pre-heated resin, can prove to be difficult and particularly with large components, time consuming and expensive.
- The object of this invention is to provide a method of producing resin articles, wherein the resin reaction rate may be increased.
- According to the present invention there is provided a method of producing resin articles from a resin reaction system comprising the step of subjecting the resin reaction system to high frequency vibration during reaction.
- The invention further provides a resin article produced from a resin reaction system subjected to high frequency vibration during reaction.
- Subjecting a resin reaction system, such as of an unsaturated polyester resin, to vibration is believed to reduce setting or gel time compared with a corresponding unvibrated system.
- Any suitable means of imparting vibration may be used including mechanical and acoustic. Improved reaction times can be achieved with vibration frequencies in the range of 5 to 500 KHz, preferably within the range 10-100 KHz, especially within the range 30 to 50 KHz and more especially within the range 35 to 50 KHz.
- The invention has application to any fabrication technique especially in relation to resin used in fibre reinforced plastics and is particularly useful in resin transfer moulding and similar processes where resin is caused to flow into a closed mould containing fibre reinforcement. The invention is also particularly useful in relation to pre-impregnated glass fabrication systems.
- The invention will now be further described with reference to the following Examples.
- A polyester resin was mixed with 25% of its weight of milled glass fibre. 1% of a 1% by weight solution of cobalt naphthenate was mixed in followed by 2% by weight of methyl ethyl ketone peroxide (50% solution). The resultant mixture was immediately poured into two identical moulds. The first of these moulds was immersed in an unstirred water bath at 22 degrees C. The second mould was simultaneously immersed in a water bath at 22 degrees C in which the water was subjected to mechanical vibrations of 35 KHz. The time taken for the first unvibrated resin to solidify was 29.5 minutes. The resin in the vibrated water bath solidified in 7.6 minutes.
- Resin containing 1% of a 1% by weight solution of cobalt naphthenate and 2% by weight of methyl ethyl ketone peroxide (50% solution) was injected into a small closed mould containing continuous filament glass mat so that the final weight ratio of resin to glass was 3:2. The system was allowed to gel and the time for this gellation was 33 minutes. The same experiment was repeated but the mould was vibrated mechanically at 30 KHz. The resin gelled in 15 minutes.
- Example 2 was repeated but with jute fibre instead of glass mat. In this Example the unvibrated sample gelled in 29 minutes and the vibrated sample gelled in 14 minutes.
- Example 2 was again repeated but with a weight ratio of resin to glass of 1:1. In this Example the resin gelled in 35 minutes when not vibrated and in 16 minutes when vibrated.
- Example 1 was repeated but using finely ground calcium carbonate instead of milled glass fibre. In this example the unvibrated sample solidified in 34 minutes and the vibrated sample solidified in 16 minutes.
- A piece of glass fibre mat was impregnated with polyester resin containing 0.5% of a 1% by weight solution of cobalt naphthenate and 0.75% by weight methyl ethyl ketone peroxide. The pre-impregnated mat was quickly sealed in a water impermeable film and forced against the inside of a clay pipe. The pipe was filled with water at 20 degrees C and the water was subjected to vibration of 50 KHz. The system gelled in 15 minutes. An equivalent system but without vibration gelled in 27 minutes.
- Example 6 was repeated but the catalyst was replaced with 0.75% by weight of Trigonox 42S - t-butyl perisononanoate and 0.75% by weight Perkadox 16 - bis - (4t-butylcyclohexyl) peroxy dicarbonate. In this case the water was warmed to 35 degrees C. The sample vibrated at 35 KHz gelled in 11 minutes, an unvibrated sample gelled in 21 minutes.
- Example 7 was repeated except that the system was vibrated at 50 KHz. In this case the resin gelled in 8 minutes compared with 11 minutes for a sample vibrated at 35 KHz and 21 minutes for an unvibrated sample.
Claims (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8819690 | 1988-08-18 | ||
GB888819690A GB8819690D0 (en) | 1988-08-18 | 1988-08-18 | Method of producing resin articles |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0356144A2 true EP0356144A2 (en) | 1990-02-28 |
EP0356144A3 EP0356144A3 (en) | 1992-04-15 |
EP0356144B1 EP0356144B1 (en) | 1995-07-19 |
Family
ID=10642372
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89308353A Expired - Lifetime EP0356144B1 (en) | 1988-08-18 | 1989-08-17 | Method of producing resin articles |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0356144B1 (en) |
AT (1) | ATE125197T1 (en) |
DE (1) | DE68923498T2 (en) |
ES (1) | ES2075051T3 (en) |
GB (2) | GB8819690D0 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4420324B4 (en) * | 1994-06-13 | 2004-02-26 | Jäger, Arnold | Plastic peg |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1055640A (en) * | 1963-12-17 | 1967-01-18 | Paul Arthur Woldemar Jurschewi | A polymerization process and plant for said process |
SU670582A1 (en) * | 1978-02-20 | 1979-06-30 | Предприятие П/Я Р-6925 | Method of producing poly-e-caproamide |
DD140121A2 (en) * | 1976-02-08 | 1980-02-13 | Karl H Junge | METHOD AND DEVICE FOR PRODUCING OBJECTS OF FIBER-REINFORCED MATERIALS |
GB2197656A (en) * | 1986-10-31 | 1988-05-25 | Mita Industrial Co Ltd | Process for producing electrophotographic toner |
-
1988
- 1988-08-18 GB GB888819690A patent/GB8819690D0/en active Pending
-
1989
- 1989-08-17 ES ES89308353T patent/ES2075051T3/en not_active Expired - Lifetime
- 1989-08-17 GB GB8918791A patent/GB2221915B/en not_active Expired - Fee Related
- 1989-08-17 DE DE68923498T patent/DE68923498T2/en not_active Expired - Fee Related
- 1989-08-17 EP EP89308353A patent/EP0356144B1/en not_active Expired - Lifetime
- 1989-08-17 AT AT89308353T patent/ATE125197T1/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1055640A (en) * | 1963-12-17 | 1967-01-18 | Paul Arthur Woldemar Jurschewi | A polymerization process and plant for said process |
DD140121A2 (en) * | 1976-02-08 | 1980-02-13 | Karl H Junge | METHOD AND DEVICE FOR PRODUCING OBJECTS OF FIBER-REINFORCED MATERIALS |
SU670582A1 (en) * | 1978-02-20 | 1979-06-30 | Предприятие П/Я Р-6925 | Method of producing poly-e-caproamide |
GB2197656A (en) * | 1986-10-31 | 1988-05-25 | Mita Industrial Co Ltd | Process for producing electrophotographic toner |
Non-Patent Citations (1)
Title |
---|
INTERNATIONAL POLYMER SCIENCE AND TECHNOLOGY, vol. 12, no. 10, 1985, page 75, Shawbury, Shrewsbury, GB; E.A. TAGIEV et al.: "Electrical method of studying the kinetics of curing of thermosets during ultrasonic moulding" * |
Also Published As
Publication number | Publication date |
---|---|
GB8918791D0 (en) | 1989-09-27 |
EP0356144B1 (en) | 1995-07-19 |
DE68923498D1 (en) | 1995-08-24 |
GB8819690D0 (en) | 1988-09-21 |
DE68923498T2 (en) | 1996-04-04 |
EP0356144A3 (en) | 1992-04-15 |
GB2221915B (en) | 1992-02-12 |
ATE125197T1 (en) | 1995-08-15 |
GB2221915A (en) | 1990-02-21 |
ES2075051T3 (en) | 1995-10-01 |
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